Disazo-dyestuffs



Unimd i fi Patent The present invention provides new, valuable disazodyestufls corresponding to the formula in which D indicates the radicalof a diazo component containing an azo group and at least onewater-solubilizing group, m a positive Whole number which is 1 or 2, R abenzene radical, if desired containing sulfonic acid groups, n apositive whole number, preferably 1, and X is a 2-halogen-4-amino-1:3z5-triazine radical attached by way of its6-position.

As such dyestuffs should primarily be mentioned those of the formula inwhich X indicates an NH group or the radical of an organic, preferablyprimary, mono amine containing at most 12 carbon atoms, R a benzeneradical and D the radical of a diazo component containing sulfonic acidgroups and having an azo group. 7

In addition to sulfonic acid groups and an azo group, the radical D cancontain further substituents such as amino-, hydroxyor nitro-groupsand/or halogen atoms. The radical D can be either anaphthylazonaphthalene radical or a naphthylazopyrazolone radical ormore preferably a benzeneazobenzene radical, a benezeneazonaphthaleneradical or a benzeneazopyrazolone radical.

The dyestufi's of the invention can be produced from the correspondingdyestuifs containing a dihalgen-, especially a2:4-dichloro-1z3:5-triazine radical by a condensation reaction in whichin such dichlorotn'azine dyestuffs one of the two chlorine atoms isreplaced by reaction with ammonia or with a primary amine, preferablycontaining at most 12 carbon atoms, whereby a corresponding radical isintroduced. The dihalogen triazine dyestuffs to be used in this case canbe obtained by methods of known type by reaction of aminodisazodyestufls of the formula in which the significance of the symbols D, m,n and R are the same as specified with reference to Formula 1 above,with cyanuric halides, especially with cyanuric chloride(2:4:6-trichloro-1z3z5atriazine) in a molecular proportion of at least1:1 or from the corresponding dyestuff components containingdischlorotriazine radicals.

ice

For the preparation of the acylatable starting dyestuffs of the Formula3, that are to be condensed with c'yanuric chloride, there are concernedas az'o components, for example the following:

2 (4'-aminobenzoyl)-amino-8-hydroxynaphthalene-6-sulfonic acid,

2 (3 aminobenzoyl)-amino-5-hydroxynaphthalene-7- sulfonic acid,

2 (4-aminobenzoylamino) -5-hydroxynaphthylene-7-sultonic acid,

2 (4' aminophenylamino)-5-hydroxynaphtalene-7-sulfonic acid,

2 (4' aminophenylamino) -5-hydroxynaphthalene-3':7-

disulfonic acid,

2 (3' aminophenylamino)-5-hydroxynaphthalene-4:7-

sulfonic acid.

As examples of aminomonoazo dyestuffs of which the diazo compounds areapplicable for coupling with these azo components, there may bementioned by way of example: 4 amino 1:1-azobenzene-3:4'-di-sulfonicacid and the dyestulis obtainable by coupling a coupling componentcontaining an NH group with diazo compounds from aminobenzene sulfonicacids, aminonaphthalene sulfonic acids, aminopyreneor -chrysene sulfonicacids, aminonaphthol sulfonic acids or aminophenol sulfonic acids, forexample the aminornonoazo dyestufis obtainable, for example, by couplingsimple diazo compounds of the benzene or naphthalene series, (forexample diazotized naphthylamines, anilines such as chlorornitranilines, toluidines, aminobenzene sulfonic acids, chlorornitraminobenzene sulfonic acids, aminobenzoic acids, nitramino benzoieacids or nitramino phenols and so on.) with m-toluidine, cresidine,3-acylamino-l-aminobenzenes, a -and fl-naphthylamine,2-amino-5-hydroxynaphthalene- 7-sulfonic acid,Z-amino-8-hydroxynaphthalene-6-sulfonic acid, or with1-hydroxy-8aaminonaphthalene-3:6-disulfonic acid.

There are also concerned as diazo components .for the preparation of thedyestuffs of the Formula 3 amino monoazo dyestuffs containing 'sulfonicacid groups such as are obtainable, for example, by coupling diazotizedmonoacyl derivatives of aromatic diamines with an azo componentcontaining an aromatic hydroxyl group or a ketomet-hylene group andsubsequent hydrolysis of the resulting acylamino-monoazo dyestuffs, forexample by hydrolysis of the aminoazo dyestuffs obtainable from phenols,naphthols, 5-pyrazolones, barbituric acids, hydroxyquinolines, fl-ketocarboxylic acid derivatives and diazotized monoacyl-diamino benzenes,monoacyl-diaminostilbene disulfonic acids and the like.

The coupling of the diazo compounds, obtained for example by means ofmineral acid, especially hydrochloric acid, and sodium nitrite, with thementioned coupling components, likewise takes place by methods of knowntype.

The condensation of the aminodisazo dyestuffs obtained from thesecomponents with cyanuric chloride is to be carried out in such a mannerthat in the resulting condensation product two replaceable halogen atomsremain of which one is replaced according to the present invention by anamino group. For purpose are concerned, in addition to ammonia, forexample methyl-, dimethyl-, ethyl-, diethyl-, propyl-, isopropyl-,butyl-, hexyl-, phenylor cyclohexyhamine, piperidine, morpholine,B-chlorethylam-ine, methoxyethylamine, -methoxy-propylamine,ethanolamines, propanolamines and acylated amines such as acetamide,butyric acid amide, urea, thiourea, hydrazine, thiosemicarbazide andtoluene sultonic acid amide, also glycocoll, amino-carbonic acid-2:5-disul-fonic acid, 1-aminobenzene-2-, -3- or -4-sul-fonic aogaoss facid, l-aminobenzene-2-, -3- or -4-carboxylic acid, 3- aminoethanesulfonic acid, aminonaphthalene sulfonic acids and N-methylamino ethanesulfonic acid.

The-condensation, according to the invention, of these amines withdihalogen triaz-ine dyestufis is advantageously carried out with the useof acid-binding agents such as sodium acetate, sodium carbonate orsodium hydroxide, and under such conditions that in the product producedone replaceable halogen atom remains i.e., for example, in organicsolvents or at relatively low temperatures in aqueous agents.

The disazo dyestuffs of this invention can likewise be prepared by meansof a modification of the process described above. This modification ofthe process consists in that the aminodisazo dyestufis applicable asstarting materials for the manufacture of the dichlorotriazinedyestufis, for example the aminodisazo dyes-tufis obtainable from thecomponents set forth above, are condensed with dihalogen triaz-ines ofthe formula i G l ialogen in which Y indicates an NH group or theradical of an amine, preferably a primary amine, containing at most 12carbon atoms.

The dihalogen triazines of the specified constitution can be prepared bymethods of known type from cyanuric halides such as cyanuric bromide orcyan-uric chloride, for example by reacting one mol of cyanuric chloridewith one mol of ammonia or with one mol of one of the amines specifiedabove The resulting dihalogen triazine compounds of the Formula 4 canfor the preparation of the disazo dyestuffs of the present invention becondensed with already prepared aminodisazo dyestufis of the specifiedtype, containing an acylatable amino group, or advantageously with theazo components applicable for the manufacture or such dyestuffs andcontaining together with the group capable of dyestulf formation also anacylatable amino group.

As examples or azo components thus obtainable, containing a4arnino-2-halogen triazine radical of the specified type and which forthe manufacture of the disazo dyestuifs of the present invention can becombined with the specified diazo compounds from amino monoazodyestuffs, there may be mentioned:

The secondary condensation products from one mol of cyanuric chlorideand one mol oi ammonia or one mol of an aminobenzene sulfonic acid andone mol of 2(4'- aminobenzoyl)-a1mino-8-hydroxynaphthalene-6 sulfonicacid, 2-(4'-aminophenyl)-amino-5-hydroxynaphthalene-7- sulfonic acid,2-(4'-am-inophenyl)-amino-5-hydroxynaphthalene-7:3'-disul fonic acid or2-(4'-aminobenzoylamino)--hydroxynaphthalene-7-sulfonic acid.

In the production of the dyestuffs of the invention by condensation ofone or the specified aminodisazo dyestu-fis with cyanuric chloride andone of the 'likewise specified simpler amines, in most cases thesequence of the condensations can be selected as dwired.

In spite ofthe presence of labile halogen atoms in the dyestufls of thisinvention they can, without loss of their valuable properties, beisolated and worked up to useful, dry dye preparations. The isolation inthe process of the invention preferably takes: place at as low atemperature "as possible by salting out and filtration. The filtereddyestuffs can be dried, desired after the addition of color stretchingagents and/or of bufler substances, for example after the addition of amixture of equal parts of monoand disodium phosphate. The drying ispreferably carried out at not too high temperatures and under reducedpressure. In some cases dry 4 preparations can be obtained directly byspray drying of the whole reaction mixture obtained according to theinvention, i.e. without intermediate isolation of the dyestufis.

The new dyestuffs of the invention are suitable for the dyeing andprinting of a wide variety of materials, especially cellulosic materialsof fibrous structure, such as linen, regenerated cellulose and primarilycotton. They are especially suitable for dyeing by the so-called paddyeing process, according to which the goods are impregnated withaqueous dyestufi solutions, if desired also containing salt, and thedyestufis fixed on the goods to be dyed, preferably in the hot, after analkali treatment. This process and the direct dye method, which is alsoapplicable in the case of many of the dyestufls obtained according tothe present process, give dyeings which as a rule are distinguished bythe purity of their color shades, by a good fastness to light andprimarily by outstanding fastness to wet processing.

Valuable and fast printings are likewise obtained by the printingprocess when the dyestuifs are fixed by heat treatment "in the presenceof alkali upon the printed goods.

When the dyestulfs contain metalwcomplex forming groups, for exampleo:o-dihydroxyazo groupings or ohydroxycarboxy groupings, as for examplein the case of salicylic acid radicals, the dyeings obtained therewithcan be'treated with agents providing metal. The treatment with theagents'providing metal can be carried out by methods of known type. Ifdesired, very valuable dyeings can be obtained by operating inaccordance with the process in which the dyeings produced with themetalfree dyestuffs are after-treated with aqueous solutions containingwater-soluble, especially complex copper compounds and basicformaldehyde condensationproducts from compounds containing in themolecule at least once the atom grouping or compounds, for examplecyanamide, that can easily be converted into such compounds.

The following examples illustrate the invention, the partsandpercent-ages being by weight unless otherwise stated and the relationbetween part by weight and part by volume being the sanne as thatbetween the kilogram and the liter. 5;

Example 1 35.7 parts of 4-amino-1:l-azobenzene-3:4'-disulfonic acid arediazotized in the presence of hydrochloric acid with 6.9 parts of sodiumnitrite. The diazo compound is coupled with a solution, alkaline withsodium bicar bonate, of 4 1 parts of 2-(4.aminoph;enyl)-amino-5hydroxynaphthaleneJ:3-disulf0nic acid. The disazo dyestufi produced --isisolated and if desired purified by redissolving and reprecipitat-ion.7.8 parts of the disazo dyestufi are dissolved in 3,000 parts or waterto a neutral solution. With ice cooling 18.4 parts of'cyanuric chloridedissolved in 50 parts of acetone are introduced and the reaction mixtureis neutralized by the gradual addition of 10% sodium carbonate solution,When the reaction is complete, 35 parts of 10% ammonia solution areadded and stirring carried out for 4 hours at 40 C. The dyestufi formedissalted out, filtered off and dried. It dyes cotton from an alkalinebath containing much salt inpure violet shades fast to When the primarydyestnfi condensation product is condensed with 17.3 parts orl-aminobenzene-ii-sulfonic acid or l-aminobenzene-Z-sulionic acid,instead of with ammonia, dyestuffs of similar properties are obtained.Inthis case the condensation can be carried out in the 5 Y presence ofan acid-binding agent; for example sodiumbicarbonate.

Referring to the following table, dyestuffs are obtained which dyecotton in the shades set forth in column IV when an condensation withcyanu-ric chloride on the are hand the compounds ofi column III and onthe other hand the aminodisazo dyestuffs obtainable by coupling the amcomponents of column II with the diazo compounds of the aminomonoazodyestufi mentioned in column I, are used.

of 17.3 parts of 1-aminobenzene-2-sulfonic acid and the reaction mixtureis neutralized by the gradual addition of about 100 parts of N-causticsoda solution. To the primary condensation product formed is added anaqueous solution, neutralized with sodium carbonate, of 33 parts of2-(4'-aminophenyl)-arnino 5-hydroxynaphthalene-7- sulfonic acid and thewhole is heated to 30 C. and in the course of 1-2 hours a dilute sodiumcarbonate solution added dropwise so that the pH remains constantbetween 5.5 and 6.5.

Into an ice cold aqueous suspension of 18.5 pants of SOsH O CH;

ll N=N' NH2 2-(4-Aminophenyl)- NHa Blue.

' amino-fi-hydroxynaphthalene-7:3- H, disulfonlo acid.

9 N=N NH: do l-Aminobenzene-Zi- Do.

sulionic acid.

i SOaH S[O;H (30H: 2 N=N- NH2 .do ..do Do.

OaH

()H 503R 4 i. N=NNH: d0 ..do D0.

HOsS- -SOsH ?H SOaH a N=N-Nm do NH: Do.

HOaS -S03H SOsH -NHQ .do Morpholine Do.

303K I l 7 N=NNH2 .do 'y-Methoxy- Do.

propylamine.

HO5S- SOaH ?H 8.0311 8 -N=N-NHZ lo 2-Amino ethanol Do.

HOaS- SOsH SOaH 11 /C=CN= O-mm .9 N j d0 1-Amino-benzene-3- Blulshviolet.

\ sulfonic acid.

N=C H0 33 I OHs Example 2 The resulting secondary condensation productis treated at 0 C. with 25 parts of sodium bicarbonate and the diazocompound obtained from 35.7 parts of 4-amino- 1:lGazobemne-kW-disulfonicacid. When the coupling is complete, the dyestuli is salted out,filtered oil and dried. It :dyes cellulose from an alkaline bathcontaining salt in pure violet shades fast to washing.

Example 3 4.6.7 parts of the aminoazo dyestufl obtained by coupling 1mol of the diazotized O-benzene-sulfony-l ester of1-amino-8-hydroxynaphthalene-3z-disulfonic acid with 1 mo] of1-'arnino-2-methoxy-S-methylbenzene, are diaz otized in hydrochloricacid solution with 6.9 parts of sodium nitrite. The diazo compound iscoupled in the presence of sodium carbonate or sodium bicarbonate with41 parts of 2-(4-aminophenyl)-amino-5-hydroirynaphthalene-7:3-disulfonic acid and from the dyestuff formed, by heating with dilutecaustic soda solution, the O-benzene-sulfonyl residue is split ofi.

A neutral solution of the aminodisazo dyestulf obtained in this manneris allowed to flow into an ice cold aqueous suspension of 184 parts ofcyanuric chloride and the reaction mixture is neutralized by the gradualaddition of dilute sodium carbonate solution. When the condensation iscomplete, 40 parts of 10% ammonia solution are introduced and the wholeis stirred for some hours at -40 C. The dyestuff formed is salted out,filtered and dried. It dyes cellulose fibers from an alkaline bathcontaining salt in pure greenish blue shades.

Dyestuffs are obtained which likewise dye cellulose in blue shades whenin the above example the ammonia used for replacement of the secondchlorine atom is subtituted by a primary aromatic amine, for example 1-aminobenzene-3-sulfonic acid, 1-aminobenZene-2-sulfonic acid or1-aminobenzene-4-sulfonic acid.

Example 4 To a neutral solution of the primary condensation HOaS ditionof sodium carbonate. The resulting dyestufi dyes cellulose fibers inblue shades fast to light and washing.

SO'aH Example 5 2 parts of the dyestufif obtainable according to thefirst paragraph of Example 1, which in the form of the free acid has theformula are dissolved in 100 parts of water by boiling.

The solution is added to 3900 parts of cold water, 40 parts of trisodiumphosphate and parts of .sodium chloride are added and 100 parts of acotton fabric are entered into this dye bath.

The temperature is raised within 45 minutes to C., a further 80 parts ofsodium chloridebeing added after 30 minutes. The temperature ismaintained for 30 minutes at 90 C. and the dyeing is then rinsed andsoaped for 15 minutes in an 0.3% boiling solutionof a non-ionic washingagent, rinsed and dried.

A pure violet dyeing fast to washing and light is obtained.

Example 6 1 part of the dyestuff obtained according to the firstparagraph of Example 1 is dissolved in parts of water. A staple fiberfabric is impregnated with the resulting solution so that its weightincreases by 75% and it is then dried.

The fabric is thereupon impregnated with a solution at 20 C. containingper liter 10 grams of sodium hydroxide and 300 grams of sodium chloride,squeezed out to an increase in weight of 75 and the dyeing steamed for60 seconds at 100-101" C., rinsed, soaped for a /4 hour in an 0.3%boiling solution of a non-ionic washing agent, rinsed and dried. Aviolet dyeing fastto washing is obtained.

By using instead of the staple fiber fabric a cotton fabric, a similargood result is obtained.

What is claimed is:

1. The disazo dyestutf which in its free acid state corresponds to theformula 2. The disazo dyestufi which in its free acid state correspondsto the formula CHI N=N C (E OCH: H018 -NH- 503E 3. The disazo dyes/cuffwhich in its firee acid state corresponds to the formula Hons N=N HO N=NCl OH OCH: HOzS- NH- SO:H

References Cited in the file of this patent UNITED STATES PATENTS2,722,527 Wehrli et a1. Nov. 1, 1955 FOREIGN PATENTS 760,085 GreatBritain Oct. 31, 1956 UNITED STATES PATENT OFFICE CERTIFICATE OFCORRECTION Patent No. 2,993,038 July 18, 1961 Alfred Fasciati et al Itis hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 1, line 72, for "dischlorotriazine" read dichlorotriazine column7, line 35, for "collulose" read cellulose columns 7 and 8, theright-hand portion of the formula in claim 2 should appear as shownbelow instead of as in the patent:

N N I! I c C-NI-I2 Signed and sealed this 2nd day of January 1962.

Attesting Officer Commissioner of Patents

1. THE DISAZO DYESTUFF WHICH IN ITS FREE ACID STATE CORRESPONDS TO THEFORMULA